Method of preparing copper fungicide solutions



Patented July 8, 1947 UNITED STATES PATENT OFFICE METHOD OF PREPARING COPPER FUNGICIDE SOLUTIONS Leo Roon, South Orange, N. J assignor to Nuodex Products 00., Inc., Elizabeth, N. J., a corporation of New York No Drawing; Application November 10, 1943, Serial No. 509,809

preservative treatment will rot quite rapidly when exposed to the attacks of fungi, such as mildew organisms. In some cases untreated cellulose fabric articles, such as sandbags, will rot in one to two weeks when subjected to conditions favorable for the growth of mildew. The same type of fabric material, when treated with certain fungicidal preservatives, will last under corresponding conditions for as long as two years.

Among the fungicides used, certain copper soaps, particularly copper. naphthenate, have been heretofore employed with great success. These copper soaps have been applied either in the form of their organic solvent solution, or by way of an aqueous emulsion. They have also occasionally been used by dissolving the soaps in 12 Claims. v(Cl. 167-22) cient as the copper naphthenate deposited by prior known procedures. 7

Among the advantages accruing from the use of the in situ method just described are the very simple and easy manipulation of the component raw materials as compared with the more diflicult way of dissolving". the taffy-like copper naphthenate salt in the ammonia. Also there is a definite saving in cost when the compound is prepared directly in the ammoniacal solution. There is no doubt therefore that, when it is desired to apply a normal copper soap in am- -moniac'al solution, the method of preparing it in situ, as hereinbefore described, possesses deflaqueous ammonia, wherein substantial solution takes place.

I have discovered that it is possible to obtain highly eificient aqueous ammonia solution of- Ea'mnple 1'; Copper carbonate (56% copper) grams 82.6 Water M 500 Ammonium hydroxide (28%) grams 210 Naphthenic acid (A. N. 235) do 347 When the solution thus obtainedwas deposited upon the fabric, wood and other cellulose articles,

it was found that the resulting deposit, upon evaporation of the ammonia and water, represented a substantially water-insoluble copper compound. When the treated articles were compared with articles treated with a. solvent solution' of copper. naphthenate of equal concentration and the treated articles were exposed to a mildewing test, theeopper compound deposited by the ammonia treatment proved at least as embe performed in simple Example 2 Copper carbonate grams.. 82.6 Water or 500 Ammonium hydroxide grams 205 Oleic acid y do 410 Example 3 Copper carbonate "grams" 82.6 'Water m 500 Ammonium hydroxide grams 200 Hydrogenated rosin -f do 445 Ewample4 Copper carbonate grams 82.6 Water m 500 Ammonium hydroxide "grams..- 2 10 Naphthenic acid-Oleic acid mixture (20% voleic) grams 360 Example 5 I Copper hydroxide grams- "71 Water cc Ammonium hydroxide grams..- 240 Benzoic acid do 177 Erampleli Copper hydroxide grams 71 Water 570 Ammonium hydroxide ..grams Naphthenic acid (A. N. 2l2) do 387 f Example 7 p I Copper carbbnate grams.... 82.6 Water M 500 Ammonium hydroxide.- grams 210 Naphthenic acid (A. N. 235) hydrogenated roan mixture of which 15% is hydro- 'genated-rosinnu ni "grams" .357

nite advantages over the method heretofore practised. v

In the foregoing example, naphthenic acid has been referred to as the acid involved in the reaction. I have also demonstrated that one or more other acids either alone or in combination with naphthenic acid, may be employed to yield satisfactory fungicides in ammoniacal solution.

' compounds.

situ of normal copper soaps in the presence of aqueous ammonia. The term "normar refers to copper soaps in which the acid radical is stoichiometrically sufficient to bring about the formation of a copper soap which is neutral, 1. e., one which is neither acid nor basic in character.

I have discovered that it is also possible and a practical to produce highly efllcient fungicides by forming in situ, in the presence of aqueous ammonia. hydroxy copper soaps. These soaps are so formulated that the amount of acid used is insumcient to form the normal or neutral The hydroxy copper soap is thus one which contains some free and unreacted OH groups. The unpredictable fact is that these hydroxy soaps perform equally as well as fungicides as do the normal copper soaps. -This is surprising and wholly unexpected because it has long been a universally accepted fact that, e. g., copper hydroxide, or copper carbonate would not protect cellulosic fabric against mildew nearly as well as copper naphthenate or copper oleate, considered, of course, on. an equal metal basis. Therefore it was not to be expected that a soap containing stoichiometrically insufficient .acid radical would perform as efliciently as the corresponding normal copper soap.

I have found that there are very tangible advantages resulting in the use of hydroxy' copper soaps as fungicides. Among these may be mentioned; substantially lower quantities of the acid radicals are required to bring about the same protective end result; due to the lower consumption of the acid radical, definite economies are obtained; less of the copper soap has to be deposited on' the fabric in order to equal the same deposited metal content in the form of the normal soap and this means less change in weight, appearance and feel of the fabric. Because of the lower amount of acid radical, lesscombustible material is present on the treated fabric with resulting lesser fire hazard. The odor of the fabric treated with the hydroxy soaps is less affected by such treatment than when the normal soaps are employed.

Examples of the formation of the hydroxy copper soaps are as follows:

Ercample 8 For normal soap 41 grams acid would be necessary. Y

Example 10- Copper carbonate "grams-.. 82.6 Water..- M 500 Ammonium hydroxide ..grams 200 Hydrogenated rosin; ..do 129 For normal soap 445 grams acid would be necessary. 1

Emamplell V Copper carbonate grams 82.6 Watch cc.- 500 Ammonium hydroxide grams 210 Naphthenic acid-oleic acid mixture (20% oleic) g'rams 129 For normal soap 360 grams acid mixture would be necessary.

- Example 12 Copper hydroxide grams "11 Water cc 570 Ammonium hydroxide grams 240' Benzoic acid do 129 For normal soap 177. grams acid would be necessary.

For normal soap 387 grams acid would be necessary.

, Example 14 Copper carbonate "grams..- 82.6 Water cc 500 Ammonium lwdroxide grams 210 Naphthenic acid (A. N. 235) hydrogenated rosin mixture of which 15% is hydrogenated rosin g-rams 129 For normal soap 357 grams acid mixture would be necessary.

It will be apparent that all of the acids hereinbefore referred to possess the following characteristics, namely: they are organic acids, substantially water-insoluble, substantially non-volatile. They are selected as to form, upon evaporation of the ammonia and water, copper soaps which are substantially water-insoluble. Any acid which will be capable of producing, in the presence of the aqueous ammonia, a copper soap soluble within such system and depositing a water-insoluble copper soap upon application of the fungicide and subsequent drying, will satisfactorily function in accordance with the present invention.

In all of the foregoing examples, ammonia was used as a component of the system. I have found it feasible, however, to employ, in place of the ammonia, certain volatile organic amines, such,

, as for example, monoamyl amine, mono-N-butyl amine, triethyl amine. These amines appear to function in the same way that the ammonia functions in carrying out this invention.

It will be apparent from the foregoing that the present invention distinguishes from all prior practice in connection with the preparation of rotproofing compositions in many particulars among which is the fundamental concept of so preparing the fungicide compositions that the reactions of all of the component parts are effected in situ, to produce the desired end product.

In place of the fungicidal copper metal in the reaction, it is possible to employ other fungicidal copper soap.

e 5. The herein described method of making-watar-insoluble copper "soap which comprises: reactingwater-insolublecopper raw material se- 1 lected from a group consisting of copper metal,

. copper hydroxide, and copper carbonate, together the ammoniacal copper soap compositions are useful and valuable in connection with phytocidal oils and like compositions. Such compositions may include, for example, in addition to the. ammoniacal copper soap, such agents as wax emulsions, resins, water-soluble waxes, and/orany other film-forming materials which would provide added valuable features to the phytocidal composition. They will, for example, improve the adhesiveness of the composition when applied to plants, other vegetation onarticles. The ammoniacal hydroxy copper soaps are useful in con- Junction with other components for the making oi anti-fouling paints and for various other uses where a water-insoluble fungicidal copper soap is desirable.

The foregoing detailed description sets forth the invention in its preferred practical form, but the invention is to be understood as fully commensurate with the appended claims.

Having thus fully described the invention, what I claim as new and desire to secure by Letters Patent is:

1. The herein described method of making wae with naphthenic acid in-the presence of aqueous ammonia, the copper raw material and the acid being present in stoichiometrical quantities to produce an aqueous ammoniacal solution of a substantially water-insoluble normal copper soap. 6. The herein described method of making water-insoluble copper soap which comprises: reacting water-insoluble' copper raw material selected from a group consisting of copper metal, copper hydroxide, and copper carbonate, together with naphthenicacid in the presence of aqueous ammonia, there being present in the reaction less acid than the stoichiometrical quantity thereof 7. The herein described methodof. making water-insoluble copper soap which comprises: re-

ter-insoluble copper soap which comprises: .re-

acting water-insoluble copper raw materialselected from a group consisting of copper metal,

copper hydroxide, and copper carbonate, together with. at least one substantially water insoluble monobasic organic acid in'thepresence of aqueous ammonia to producein situ an aqueous ammoniacal solution ofa substantially water-inacting water-insoluble copper raw material selected from a group consisting of copper metal,

. copper hydroxide, and-copper carbonate, together 'monia, the copper raw material and the acid being present in stoichiometrical quantities toproduce an aqueous ammoniacal solution of a substantially, water-insoluble normal copper soap.

9. The herein described method of making water-insoluble copper soap which comprises: reacting water-insoluble copper raw material selected from a group consistin of'copper metal, copper hydroxide, and copper carbonate,,together -with oleic acid in the presence of aqueous amcopper hydroxide, and copper carbonate, together 'with atleast one substantially water-insoluble monobasic organic acid in the presence of aqueous ammonia, the copper raw material and the v v a'cid being present in stoichiometric quantities to produce an aqueous ammoniacal solution of a substantially water-insoluble copper soap.

- lected from a group consisting ofcopper metal,

3. The herein described method of makingwater-insoluble copper soapwhich comprises: reacting water-insoluble copper raw material'selected from a group consisting of copper metal,

copper hydroxide, and copper carbonate, together. with at least one substantially water-insoluble monobasic organic acid in the presence of aqueous ammonia, there being present in the reaction less acid than the stoichiometrical quantity there-.

-.of necessary to produce a normal copper soap, whereby an aqueous ammoniacal solution of a withnaphthenic acid in the'presence of aqueous ammonia to produce in situan aqueous ammoniacal solution of a substantially water-insoluble monia, there being present in the reaction less acid than the stoichiometrical quantity'thereof necessary to produce a normal copper soap, whereby an'aqueous ammoniacal solution of a hydroxy'copper soap'is obtained.

'10.Th herein described method of making water-insoluble copper soap which comprises: reacting water-insoluble copper raw material secopper hydroxide, and coppercarbonate, together 'with hydrogenated rosin in the presence of aqueous ammonia to produce in situ an aqueous ammoniacal solution of a substantially water-insolubIecoppersoap; t

11. The herein described method of making water-insoluble copper soap which comprises: reacting water-insoluble copper raw material selected from a group consisting of copper metal, copper hydroxide, and copper carbonate, together with hydrogenated rosin in vthe'presenc of aqueou ammonia,.the copper raw material and .the

acid being present in stoichiometrical quantities to produce an aqueous ammoniacal solution of a substantially water-insoluble normal copper soap.

12. The herein described method of making .water-insoluble copper soap which comprises: re-

' acting waterinsoluble copper raw material sewith hydrogenated rosin in the presence of aqueone ammonia, there being present in the reaction 3 less acid than the stoichiometrical quantitythereof necessary to, produce anormal copper soap,

whereby 'an aqueous emmonlacal Solution 'of a, hy- 'fiumber file of this patent: r K V UNITED STATES PATENTS Number Name Date 993,921 Ellis May 30, 1911 1,482,416 Snelling Feb. 5, 1924 Name Date Hedenburg June 22, 1926 Mlnich May 3, 1938 Gordon 'Mar. 7, 1939 Baker May 9, 1939 Belzer Nov. 23, 1943 Minlch Jan. 30, 1945 OTHER REFERENCES 10 Fullerton, Chemical Abstracts, v01. 36, 1942,

pag 1498. 

